Substituted alpha,alpha-dichloromethane-sulfenyl chlorides and their manufacture

ABSTRACT

ALPHA-CARBAMOYL-ALPH, ALPH-DICHLORO-METHANE-SULFENYL CHLORIDES AND THEIR METHOD OF MANUFACTURE, WHICH COMPOUNDS ARE PESTICIDALLY ACTIVE AND OR ARE USEFUL PRECURSORS FOR A VARIETY OF PESTICIDES.

United States Patent Oflice 3,770,824 Patented Nov. 6, 1973 ABSTRACT OF THE DISCLOSURE Alpha-carbamoyl-alpha,alpha-dichloro-methane-sulfenyl chlorides and their method of manufacture, which compounds are pesticidally active and/ or are useful precursors for a variety of pesticides.

This invention relates to the manufacture of new and useful alpha,alpha-dichloro-methanesulfenyl chlorides of the formula \N(HJC 01,-s-c1 from a substituted sulfide of the formula and sulfuryl chloride or chloride, and intermediary products obtained therein described hereinafterwards, wherein A is alkylene of the empirical formula C H wherein n is a whole number from 4 to 8, inclusive, and having from 4 to 8, inclusive, carbon atoms in a continuous chain between the terminal valence bonds, B is hydrogen, alkyl of from 1 to 5 carbon atoms, alkoxyalkyl of from 2 to 6 carbon atoms, cyclopentyl, cyclohexyl, naphthyl, phenyl or substituted phenyl wherein the ring substituents thereof total from 1 to 3 which substituents are from 0 to 3 alkyl of from 1 to 6 carbon atoms, from 0 to 2 alkoxy of from 1 to 6 carbon atoms, from 0 to 3 halogen of atomic weight in the range of 18 to 80, from 0 to 2 nitro, from O to 1 cyano, or from 0 to 2 trifiuoromethyl, D is hydro gen, alkyl of from 1 to 6 carbon atoms, alkoxyalkyl of from 2 to 6 carbon atoms, cyclopentyl, cyclohexyl, naphthyl, phenyl and substituted phenyl wherein the ring substituents thereof total from 1 to 3, from 0 to 3 alkyl of from 1 to 6 carbon atoms, from 0 to 2 alkoxy of from 1 to 6 carbon atoms, from 0 to 3 halogen of atomic weight in the range of 18 to 80, from 0 to 2 nitro, from 0 to 1 cyano, or from 0 to 2 trifluoromethyl, and R is hydrogen, methyl or benzyl. Examples of pyrrolidinyl, piperidinyl, hexamethyleneimino, heptamethyleneimino, octamethyleneirnino, Z-ethylpyrrolidinyl, 3-nbutylpyrrolidinyl, 2-5-dimethylpyrrolidinyl, 2,5 diethylpyrrolidinyl, 3,4 dimethylpyrrolidinyl, 2-pipecolinyl, 3- pipecolinyl, 4-pipecolinyl, 2,6-dimethylpiperidinyl, Z-ethyl- G-methylpiperidinyl, 2-n-propylpiperidinyl, 3-methylhexamethyleneimino, 3,4 dimethylhexamethyleneimino, and the various isomeric forms thereof. It is preferred that A have from 4 to 6, inclusive, carbon atoms in a continuous chain between the terminal valence bonds. Examples of include Anilino N-methylanilino Nethylanilino N-isopropylanilino N-isobutylanilino N-n-amylanilino N- (methoxymethyl -anilino N- ethoxyethyl) -anilino N-(isobutoxymethyl) -anilino N- (n-butoxyethyl) -anilino N- 3-methoxypropyl -ani1ino N-ethyl-3-chloro anilino N-isopropyl-2,S-dichloroanilino N-methyl-3,4-dichloroanilino N-isopropyl-2,4,S-trichloroanilino N-rnethyl-2,4,6-trichl0roanilino N-isopropyl-Z,5-dichloro-4-bromoanilino N-isoamyl-2,6-dichloro-4-bromoanilino N-n-prop yl-2-bromoanilino N-ethyl-4-fluoroanilino N-methyl-2-chloro-4-fluoroanilino N-ethyl-2,6-dichloro-4-fiuoroanilino 3-chloroanilino 2,5 -dichloroanilino 4-cyanoanilino 3,4-dichloroanilino 2,4,5 -trichloroanilino 2,4,6-trichloroanilino 2,5 -dichloro-4-bromoanilino 2,6-dichloro-4-bromoanilino 2-bromoanilino 4-fluoroanilino 2-chloro-4-fluoroanilino 2,6-dichloro-4-fiuoroanilino Amido N-methyl-amido N-ethyl-amido N-isopropyl-amido N-isobutyl-amido N-n-amyl-amido N- (methoxymethyl -amido N- ethoxyethyl -amido N- (isobutoxymethyl -amid0 N- (n-butoxyethyl -amido N-( 3-methoxypropyl -amido N-methyl-N-ethylamido N-methyl-N-isopropylamido N-methyl-N-isobutylarnido N-ethyl-N-isopropylamido N,N-dimethylamido N,N-diethylamido N,N-diisopropylamido N,N-diisobutylamido N,N-diamylamido N,N-di methoxymethyl) amido N,N-di ethoxyethyl) amido N,N-di isobutoxymethyl amido N,N-di (n-butoxyethyl) amido N,N-di 3-methoxypropyl) amido and the like. It is preferred that, when B is naphthyl, phenyl or substituted phenyl, D is hydrogen.

Preferred substituted phenyls have the formula wherein X is halo, tert-alkyl of from 4 to 6 carbon atoms (for example tert-butyl, tert-pentyl and l,l,-dimethylnbutyl), wherein Y is halo or primary or secondary alkyl having not more than 4 carbon atoms (for example, methyl, ethyl, n-propyl, n-butyl, isobutyl, isopropyl or see. butyl) and wherein Z is halo, hydrogen or primary or secondary alkyl having not more than 4 carbon atoms (for example, methyl, ethyl, n-propyl, n-butyl, isopropyl or sec.butyl). Preferred halo are chloro and bromo.

The compounds of this invention are conveniently and efficiently manufactured by reacting in an inert organic liquid medium one molecular proportion of substituted sulfide of the formula wherein R is benzyl, methyl or hydrogen but preferably hydrogen with at least three molecular proportions of chlorine or sulfuryl chloride at a reaction temperature above the freezing point of the reaction system. The mechanics of this reaction is not completely understood but can be represented by the following chemical equations.

Under mild reaction conditions when R is benzyl or methyl the reaction apparently proceeds in a stepwise fashion which permits the intermediary product to be recovered. The reaction is postulated as follows:

Cir

N --C0lzSCl HCll RC1 25021 As noted above, it is preferred that R is hydrogen. When -R is hydrogen there is no need for an additional step to remove RC1 from the product since HCl is a gas at normal reaction temperatures and readily volatilizes from the system.

A precursor sulfide of the formula where R is H is readily prepared from the corresponding primary or secondary amine and thioglycolic acid as follows:

where R is C H CH or CH a precursor sulfide is prepared from the corresponding alpha halo acetanilide or acetamide and benzyl mercaptan or methyl mercaptan as follows:

X is halo, preferably iodo, chloro or bromo, and more preferably chloro or bromo. Alpha halo acetanilides or acetamides are commercially available compounds or may be readily prepared from available compounds by known methods. In place of the benzyl or methyl mercaptan which forms the corresponding mecaptide in the presence of a base it may be convenient under certain conditions to use the corresponding sodium mercaptide initially in the above reactions.

The reaction conditions under which alpha-carbamoylalpha, alpha-dichloro-methane sulfenyl chlorides and intermediate products, as described above, are obtained are generally the same. The reaction is normally carried out at a temperature above the freezing point of the system but preferably below the boiling point of the inert organic liquid. Still more preferably, the reaction is carried out at temperatures of from about 0 degrees centigrade to about degrees centigrade. Since gaseous reaction products are evolved, the reaction is usually carried out at atmospheric pressure, but higher or lower pressures may be utilized if equipment and other factors favor such higher or lower pressures. The reaction may be carried out in an open vessel or under reflux.

The inert organic liquid employed in the overall manufacture of this invention or any portion thereof can be any organic liquid, or mixtures thereof, which is inert under the reaction conditions, and preferably that having a boiling point in the range of from about 30 C. to about C. Ordinarily, the inert organic liquid comprises liquid alaknes or liquid chloroalaknes or various mixtures thereof, for example; n-pentane, 3-ethylpentane, n-hexane, 2-ethylhexane, n-heptane, dichloromethane, 1,1-dichloroethane, chloroform, carbon tetrachloride, isobutyl chloride, and various mixtures thereof. Under certain mild reaction conditions where temperature level is readily controllable, sulfuryl chloride itself may be used as the organic liquid. In general, it is preferable but not necessary that the amount of said inert organic liquid present throughout the course of the reaction be that at least sufficient to maintain the intermediary compounds in solution. It is more preferred that said hydrocarbons contain at least one chloro or bromo and have from 1 to 3 carbon atoms. Still more preferred inert organic liquids include 1,2-dichloroethane, chloroform, and methylene chloride. Even still more preferred as an inert organic liquid is methylene chloride.

When R is methyl or benzyl, the level of chlorine or sulfuryl chloride charged to the reaction system determines whether an alpha-carbamoyl-alpha,alpha-dichloromethane sulfenyl chloride or an intermediary product is obtained. When less than 3 moles of chlorine either as gaseous chlorine or as sulfuryl chloride per mole of substituted sulfide is charged to the reaction system the intermediary product is the major reaction product. When more than 3 moles of chlorine either as gaseous chlorine or as sulfuryl chlorine per mole of substituted sulfide is charged to the reaction system, alpha-substituted carbamoyl alpha,alpha-dichloro-methane sulfenyl chloride is the major reaction product. Since the chlorination appears to proceed in a step-wise fashion, the intermediary product may likewise be obtained even at higher levels of chlorine when reaction conditions are mild; i.e., the temperature is maintained below about degrees centigrade and reaction time does not exceed about one hour.

Alpha-substituted car'bamoyl alpha,alpha-dichloromethane sulfenyl chlorides exhibit herbicidal activity toward noxious weeds and have particular utility as selective preemergent herbicides.

As illustrative of this invention, but not limitative thereof is the following:

EXAMPLES 1 THROUGH 8 These examples illustrate the preparation of substituted sulfides having the formula wherein R is hydrogen which sulfides are precursors to the compounds made by the method of this invention.

Example 1 To a suitable reaction vessel equipped with a thermometer, agitator and venting means are charged approximately 62 parts by weight of 2,6-dimethylaniline (about /2 mole) and approximately 46 parts by weight of thioglycolic acid (about /2 mole). The contents of the so-charged vessel are heated with agitation under a nitrogen atmosphere to about 130 degrees centigrade and maintained at that temperature for about 3 hours. The contents are cooled to about room temperature and washed with a dilute aqueous HCl solution. A white solid (melting point of 101 to 109 degrees centigrade) is isolated by filtration and identified as alpha-mercapto- 2',6'-dimethylacetanilide.

Alpha-mercapto-Z,6-dimethylacetanilide exhibits preemergent herbicidal activity against Johnson grass.

Example 2 To a suitable reaction vessel equipped with a th'ermometer, agitator and venting means are charged approximately 93 parts by weight of aniline (about 1 mole) and approximately 92 parts by weight of t-hioglycolic acid (about 1 mole). The contents of the so-charged vessel are heated with agitation under a nitrogen atmosphere to about 130 degrees centigrade and maintained at that temperature for about 4 hours. The contents are cooled to about room temperature and washed with a dilute aqueous HCl solution. A white solid is isolated by filtration, dissolved in and recrystallized from chloroform, and identified as alpha-mercapto-acetanilide (melting point of 107 to 110 degrees centigrade).

Example 3 To a suitable reaction vessel equipped with a thermometer, agitator and venting means are charged approximately 64 parts by weight of para-chloroaniline (about /2 mole) and approximately 46 parts by weight of thioglycolic acid (about /2 mole). The contents of the socharged vessel are heated with agitation under a nitrogen atmosphere to about 130 degrees centigrade and maintained at that temperature overnight. The contents are cooled to about room temperature and washed with a dilute aqueous I-ICl solution. A white solid is isolated by filtration, dissolved in and recrystallized from a mixed solvent of chloroform and ethanol and identified as alphamercapto-para-chloroacetanilide (melting point of 127 to 129 degrees centigrade).

Alpha-mercapto-para-chloroacetanilide exhibits preemergent herbicidal activity against Canada thistle.

Example 4 To a suitable reaction vessel equipped with a thermometer, agitator and venting means are charged approximately parts by weight of meta-trifluoromethyl aniline (about /2 mole) and approximately 45 parts by weight of thioglycolic acid (about /2 mole). The contents of the so-charged vessel are heated with agitation under a nitrogen atmosphere to about 130 degrees centigrade and maintained at that temperature for about 3 hours. The contents are cooled to about 0 degrees centigrade and washed with a dilute aqueous HCl solution. A white solid is isolated by filtration and identified as alphamercapto-meta-triiluoromethylacetanilide (melting point of 35 to 40 degrees centigrade) Alpha-mercapto-meta-trifluoromethylacetanilide exhibits pre-emergent herbicidal activity against Canada thistle and Johnson grass and contact herbicidal activity against Canada thistle, cocklebur and lambsquarter.

Example 5 To a suitable reaction vessel equipped with a ther mometer, agitator and venting means are charged approximately 75 parts by weight of 2,6-diethylaniline (about /2 mole) and approximately 46 parts by Weight of thioglycolic acid (about /2 mole). The contents of the so-charged vessel are heated with agitation under a nitrogen atmosphere to about 130 degrees centigrade and maintained at that temperature overnight. The contents are cooled to about room temperature and washed with a dilute aqueous HCl solution. A white solid is isolated by filtration, dissolved in and recrystallized from ethanol, and identified as alpha-mercapto-Z',6'-diethylacetanilide (melting point of 120 to 124 degrees centigrade).

Alpha-mercapto-2',6'-diethylacetanilide exhibits preemergent herbicidal activity against velvet leaf and lambsquarter.

Example 6 To a suitable reaction vessel equipped with a thermometer, agitator and venting means are charged approximately 123 parts by weight of para-anisidine (about 1 mole) and approximately parts by weight of thioglycolic acid (about 1 mole). The contents of the so-charged vessel are heated with agitation under a nitrogen atmosphere to about 130 degrees centigrade and maintained at that temperature for about 3 hours. The contents are cooled to about room temperature and washed with a dilute aqueous HCl solution. A white solid is isoiated by filtration and identified as alpha-mercapto para-methoxyacetanilide (melting point of 111 to 115 degrees Centigrade) Alpha-mercapto-para methoxyacetanilide exhibits pre emergent herbicidal activity against lambsquarter and Johnson grass.

Example 7 To a suitable reaction vessel equipped with a thermometer, agitator and venting means are charged approximately 107 parts by weight of para-toluidine (about 1 mole) and approximately 92 parts by weight of thioglycolic acid (about 1 mole). The contents of the so-charged vessel are heated with agitation under a nitrogen atmosphere to about 130 degrees centigrade and maintained at that temperature for about 3 hours. The contents are cooled to about room temperature and Washed with a dilute aqueous HCl solution. A white solid is isolated by filtration and identified as alpha-mercapto-para-methylacetanilide (melting point of 117 to 123 degrees centigrade). Alpha-mercapto-para-methylacetanilide exhibits pre-emergent herbicidal activity against velvet-leaf.

Example 8 In similar fashion, other substituted sulfides having the formula shown in column A may be prepared from thioglycolic acid and the corresponding amine shown in column B. The preparation may be carried out by the procedure of Example 4 except that in place of 80 parts by weight of meta-trifiuoromethylaniline an equimolecular portion (about /2 mole) of the secondary amine of column B is added in order to obtain the sulfide of column A.

N,N-di (isobutoxymethyl) -alphamercapto-aeetarnide. N,N-diamyl-alpha mereapto-acetamide- Dimnylamine.

Di (isobutoxymethyDamine.

N,N-diisobutyl-alpha-mercapto- Diisobutylamine.

acetamide.

N -(3-methoxypropyl) -alpha-mercapto- B-methoxypropylamine.

acetamide.

N-n-an1yl-alpha-mercapto-aeetamide n-Amylamme.

Nethyl-N-isopropyl-alpha-mercapto- N ethyl-N -isopropylamine.

acetamide. p

N -(mercaptoaeetyl)pyrrolidine Pyrrolidme.

EXAMPLES 9 THROUGH 18 These examples illustrate the preparation of substituted sulfides, having the formula N-CCHflSR wherein R is methyl or benzyl, which sulfides are precursors to the compounds made by the method of this invention.

Example 9 while approximately parts by weight of chloroacetyl chloride is slowly added to the solution. Upon completion of this addition the temperature of the vessel is allowed to rise to about room temperature. The contents of the reaction vessel are extracted with chloroform by suitable means and the aqueous phase is discarded. The chloroform is distilled off and the remaining oil is dissolved in pentane. Upon cooling a white precipitate appears which is isolated by filtration and identified as N,N-diisopropyl-alphachloroacetamide (melting point of 48 to 49 degrees centigrade).

In similar fashion other N-substituted alpha-chloro or bromoacetamides may be prepared as precursors for other substituted sulfides of the formulas used in the method of the present invention.

To a suitable reaction vessel equipped with a thermometer and agitator charged with an aqueous solution containing approximately 200 parts by weight of water and approximately 19 parts by weight of sodium hydroxide is added with agitation approximately 58 parts by weight of benzyl mercaptan. Thereafter approximately 82.6 parts by Weight of N,N-diisopropyl-alpha-chloro-acetamide is slowly added with agitation. Thereupon the mass is heated on a steambath and agitated for about one hour. Thereafter the mass is cooled to about room temperature and extract ed with methylene chloride. The methylene chloride is distilled oif leaving an oily residue. The residue is dissolved in pentane, crystallized by cooling in Dry Ice, isolated by filtration and identified as alpha-(benzylrnercapto)-N,N-diisopropylacetamide (melting point of 34 to 37 degrees centigrade.)

Alpha-benzylmercapto)-N,N-diisopropylacetamide exhibits pre-emergent herbicidal activity against morning glory and Johnson grass as Well as insecticidal activity against southern corn rootworm.

Example 10 To a suitable reaction vessel equipped with a thermometer and agitator charged with an aqueous solution containing approximately 200 parts by weight of water and approximately 7.1 parts by weight of sodium hydroxide is added with agitation approximately 21.9 parts by weight of benzyl mercaptan. Thereafter approximately 50 parts by weight of alpha-bromo-2'tert-butyl 6 methylacetanilide dissolved in ethanol is slowly added with agitation. The vessel warms and a precipitate forms. Thereupon the mass is heated on a stearnbath and agitated until the precipitate dissolves. Thereafter the mass is cooled to room temperature and the precipitate reforms. A white crystalline solid is isolated by filtration and identified as alpha- (benzylrnercapto -2-tert-butyl6'-methylacetanilide (melting point of 127 to 129 degrees centigrade).

Alpha-(benzylmercapto)-2'-tert-butyl 6' methylacetanilide exhibits pre-emergent herbicidal activity against Canada thistle, cocklebur, velvet leaf, lambsquarter, smartweed, nutsedge, quackgrass, bromegrass (cheat) and barnyard grass.

Example 11 To a suitable reaction vessel equipped with a thermometer and agitator charged with an aqueous solution containing approximately 200 parts by weight of water and approximately 21 parts by weight of sodium hydroxide is added with agitation approximately 62 parts by weight of benzyl mercaptan. Thereafter approximately 60.5 parts by weight of N,N-dimethyl-alpha-chloroacetamide is slowly added with agitation. Thereupon the mass is heated on a steam bath and agitated for about one hour. Thereafter the mass is cooled to about room temperature and extracted with methylene cldoride. The methylene chloride is distilled oif leaving an oily residue. The residue is dissolved in pentane, crystallized by cooling in Dry Ice, isolated by filtration and identified as N,N-dimethyl-alpha- (benzylmercapto)-acetamide (melting point of 27 to 30 degrees centigrade).

N,N-dimethyl-alpha-(benzylmercapto) acetamide exhibits insecticidal activity against southern corn rootworm.

Example 12 To a suitable reaction vessel equipped with a thermometer and agitator charged with an aqueous solution containing approximately 200 parts by weight of water and approximately 28 parts by weight of potassium hydroxide is added with' agitation approximately 62 parts by weight of benzyl mercaptan. Thereafter approximately 105 parts by weight of alpha-chloro-N-isopropylacetanilide in ethanol solution is slowly added with agitation. Thereupon the mass is refluxed with agitation overnight. Thereafter the mass is cooled to about room temperature and extracted With methylene chloride. The methylene chloride is distilled off leaving an oily resdiue. The residue is dissolved in pentane, crystallized by cooling in Dry Ice, isolated by filtration and identified as alpha-(benzylmercapto)-N-isopropylacetanilide (melting point of 39 to 41 degrees centigrade).

Alpha-(benzylmercapto) N isopropylacetanilide exhibits pro-emergent herbicidal activity against quackgrass and barnyard grass.

Example 13 To a suitable reaction vessel equipped with a thermometer and agitator charged with aqueous solution containing approximately 40 parts by weight of Water and approximately 40 parts by weight of sodium hydroxide is added with agitation approximately 63 parts by weight of benzyl mercaptan. Thereafter approximately 134 parts by Weight of alpha-chloro-N-methoxymethyl-2',6'-diethylacetanilide dissolved in ethanol is slowly added with agitation. The vessel warms and a precipitate forms. Thereupon the mass is heated on a steam bath and agitated until the precipitate dissolves. Thereafter the mass is cooled to room temperature and extracted with methylene chloride by suitable means. The methylene chloride is distilled off and the remaining oil is dissolved in petroleum ether. Upon cooling with Dry Ice to about 70 degrees centigrade, a white precipitate appears which is isolated by filtration and identified as alpha-(benzylmercapto)-Nmethoxymethyl- 2',6'-diethylacetanilide (melting point of 33 to 35 degrees centigrade).

Alpha-(benzylmercapto) N methoxymethyl-2,6-diethylacetanilide exhibits pre-emergent herbicidal activity against velvet leaf, nutsedge, quackgrass and bromegrass (cheat) as well as insecticidal activity against southern corn rootworm.

Example 14 Alpha-(methylmercapto)-N,N-diisopropylacetamide is prepared according to the procedure of Example 9 except that in place of 58 parts by weight of benzyl mercaptan an equimolecular amount of methyl mercaptan is added.

Example 15 Alpha-(methylmercapto) 2 tert-butyl-6'-methylacetanilide is prepared according to the procedure of Example except that in place of 21.9 parts by weight of benzyl mercaptan an equimolecular amount of methyl mercaptan is added.

Example 16 N,N dimethyl alpha- (methylmercapto)-acetamide is prepared according to the procedure of Example 11 except that in place of -62 parts by weight of benzyl mercaptan an equimolecular amount of methyl mercaptan is added.

III

1 0 Example 17 Alpa-(methylmercapto)-N-isopropylacetanilide is prepared according to the procedure of Example 12 except that in place of 62 parts by weight of benzyl mercaptan an equimolecular amount of methyl mercaptan is added.

Example 18 Alpha (methylmercapto) N-methoxymethyl-2,6'-diethylacetanilide is prepared according to the procedure of Example 13 except that in place of 63 parts by Weight of benzyl mercaptan an equimolecular amount of methyl mercaptan is added.

In similar fashion other substituted sulfides, having the formula wherein R is methyl or benzyl, may be prepared from the corresponding alpha haloacetanilide or acetamide and benzyl or methyl mercaptan.

EXAMPLES 19 THROUGH 31 These examples illustrate the preparation of intermediary products having the formula wherein R is methyl or benzyl.

Example 19 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 11.6 parts by weight of alpha-(benzylmercapto)-N-isopropylacetanilide dissolved in approximately 275 parts by weight of methylene chloride. While agitating the socharged mass at about 0 C. is slowly added approximately 5.36 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. Upon completion of the sulfuryl chloride addition the mass is agitated for about one half hour at about room temperature. Thereafter the mass is stripped of volatiles under vacuum to give a solid residue which is identified as alpha-chloroalpha-(benzylmercapto)-N isopropylacetanilide (melting point of 86 to 87 degrees centigrade).

Alpha chloro alpha (benzylmercapto)-N-isopropylacetanilide exhibits pre-emergent herbicidal activity against smartweed and barnyard grass.

Example 20 The procedure of Example 19 is followed except that the reaction is carried out under reflux and, instead of charging to the system 5.36 parts by weight of sulfuryl chloride, chlorine gas is bubbled through the refluxing mass until approximately 2.9 parts by weight thereof is absorbed. Alpha chloro alpha-(benzylmercapto)-N-isopropylacetanilide is obtained.

Example 21 The procedure of Example 19 is followed except that in place of 11.6 part by weight of alpha-(benzylmercapto)- N-isopropylacetanilide an equimolecular proportion of alpha (methylmercapto) N isopropylacetanilide is dissolved in methylene chloride, alpha-chloro-alpha-(methylmercapto)-N-isopropylacetanilide is obtained.

EXAMPLES 22 THROUGH 31 The procedure of Example 19' is followed except that in place of 11.6 parts of alpha-(benzylmercapto)-N-isopropylacetanilide an equimolecular proportion of the com- 1 1 pound of column A is dissolved in methylene chloride and the compound of column B is obtained.

Ex. No. A B

22 Alpha-(benzylmeri-apto)- N,N-diisopropylacetae. 31... N-[alpha-(methylmer- Alpha-chloro-alpha-(benzylmorcapto)-N,N-diispropylacetamide.

Alpha-chloro-alpha-(benzylmercapto)-2terL-butyl6n1ethylacetanilide.

N ,N-dimothyl-alpha-chloroalpha-(benzylmereapto)- acetamide.

Alphachl0r0-alpha-(bonzyirnercapto) N'methoxyinethyl'2,6'- diethylacetanilide.

Alpha-ehloro-alpha-(methylmercapto) N ,N -diisopr0pylacet-anude. Alpha-chl0ro-aipha(methylmen capto-2-tertbutylfi-methyl acetanilide. N,N-dimethyl-alpha-ehloroa1pha-(rnethylmercapto) acetamide. Alphaehloro-alpha-(methylmercapto) -N-m eth oxymethyl-2,6'- diethylacetanilide. N-[alpha-chloro-alpha-(benzyI mercaptoracetyllpyrroli dine. N-[alpha-ehloro-alpha-(methyimercapto) -aeetyl]pyrr0lidine.

capto)-acetyl1pyrrolidine.

EXAMPLES 32 THROUGH 44 These examples illustrate the preparation of compounds of this invention having the formula wherein N is A N V and A is alkylene of the empirical formula C H wherein n is a Whole number from 4 to 8 inclusive, and having from 4 to 8 carbon atoms in a continuous chain between the terminal valence bonds from a substituted sulfide of the formula wherein A is as defined above and R is hydrogen, methyl or benzyl and sulfuryl chloride and chlorine.

Example 32 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 23.5 parts by weight of N- [alpha- (benzylmercapto)- acetyljpyrrolidine dissolved in approximately 300 parts by weight of 1,2-dichloroethane. While agitating the socharged mass at about 0 C. is slowly added approximately 40 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about C. Upon completion of the sulfuryl chloride addition, the mass is agitated for about three hours at about room temperature. Thereafter, the mass is stripped of volatiles under vacuum to give a residue which residue is dissolved in petroleum ether solvent, crystallized by cooling the solution to about 70 degrees centigrade, separated from the solvent by filtration and identified as N- [alpha,alphadichloro-alpha- (chloromercapto)-acetyl]pyrrolidine.

Example 33 The procedure of Example 32 is followed except that in place of N-[alpha-(benzylmercapto)-acetyl]pyrrolidine an equimolecular proportion of N-[alpha-(methylmercapto)-acetyl]pyrrolidine is dissolved in 1,2-dichloroethane. N- alpha,alpha-dichloroalpha chloromercapto acetyl]pyrrolidine is obtained.

12 Example 34 The procedure of Example 32 is followed except that in place of N-[alpha-(benzylmercapto)-acetyl]pyrrolidine a equimolecular proportion of N-(alpha-mercapto-acetyl) pyrrolidine is dissolved in 1,2-dichloroethane. N-[alpha,- alpha-dichloro-alph achloromercapto -acetyl] pyrrolidiue is obtained.

Example 35 The procedure of Example 32 is followed except that the reaction is carried out under reflux and, instead of charging to the system parts by weight of sulfuryl chloride, chlorine gas is bubbled through the refluxing mass until approximately 21 parts by weight thereof is absorbed. N- alpha,alpha-dichloro-alpha- (chloromercapto)- acetyl]pyrrolidine is obtained.

In similar fashion N-[alpha,alpha-dichloro-alpha- (chloromercapto)-acetyl]pyrrolidine may be prepared from N-(alphamercapto-acetyl)pyrrolidine and from N- [alpha-(methylmercapto)-acetyl]pyrrolidine.

EXAMPLES 36 THROUGH 44 The procedure of Example 32 is followed except that in place of N- [alphabenzylmercapto -acetyl] pyrrolidine in the amount of about 235 parts by weight, an equimolecular proportion of the compound shown in column A is added. By this method, the corresponding chlorinated compound of column B is prepared.

Ex. No. A B

N -[a1pha,a1ph a-diehloro-alpha- (ehloromercapto) -aeetyl]- piperidine.

Nialpha,alpha-diehloro-alpha- (chloromercapto)-acetyl]hexamethylenelmine.

N-{alpha,alpha-diohloro-alpha- 36..-" N-(alpha-rnereaptoacetyl)- pipen'dine 37-.." N-[alpha-(methylmercapto)- acetyl1hexamethyleneimine.

38"..- N -lalpha-(benzyhuercapto)- aeetyllheptamothylenei- (chloromercapto)-aeetyl]heptamine. methyleneimine.

39. N-[alpha-(methylmsrcapto)- N-[alpha,a.1pha-dichloro-alphaacety112-ethylpyrrolidine. (ehloromercapto)-aeetyl]2- ethylpyrrolidine.

N -Ealpha,alpha-di chloroalpha- (chloromercapto)-acetyl]2,5- dimethylpyrrolidine.

N-[alpha,alpha-diehloro-alpha- 40.-- N-(alpha-mercaptoacetyl)2,5-

dimethylpyrrolidine.

41..--.. N-[alpha-(benzylmereapto)- aeetyl12-ethyl-6-methyl- (chloromeroapto)-acetyl]2- piperidine. ethyl-G-methylpiperidine. 42 Nlalpha-(methylmercapto)- N-[alpha,alpha-dichloro-alphaaeetylM-pipeeoline. (ehloromercapto)-acetyl]4- pipeeoline. 43.--" N-(alpha-mercaptoaeetyl)-3,4- N-[alpha,alpha-diehloro-alphadimethylhexamethylimine. (ehlorornercapto)-aeetyl]3,4-

dimethylhexamethyleueimine.

N -[alpha, alpha-diehloro-alph a- (ch10rornereapto)-acetyll3 pipecoline.

44. N -lalpha-(benzyhnereapto)- acetyl13-pipecoline.

EXAMPIJES 45 THROUGH 72 These examples illustrate the preparation of compounds of this invention having the formula and B is hydrogen, alkyl of from 1 to 5 carbon atoms, alkoxyalkyl of from 2 to 6 carbon atoms, cyclopentyl, cyclohexyl, naphthyl, phenyl or substituted phenyl wherein the ring substituents thereof total from 1 to 3 which substituents are from 0 to 3 alkyl of from 1 to 6 carbon atoms, from 0 to 3 halogen of atomic weight in the range of 18 to 80, from 0 to 2 nitro, or from O to 2 trifiuoromethyl and D is hydrogen, alkyl of from 1 to 5 carbon atoms, alkoxyalkyl of from 2 to 6 carbon atoms, cyclopentyl, cyclohexyl, naphthyl, phenyl and substituted phenyl wherein the ring substituents thereof total from 1 to 3, from 0 to 3 alkyl of from 1 to 6 carbon atoms, from 0 to 3 halogen of atomic Weight in the range of 18 to 80, from to 2 nitro, an d irom 0 to 2 trifluoromethyl from a substituted sulfide of the formula N- CH2S-R wherein B and D are as defined above and R is hydrogen, methyl or benzyl and sulfuryl chloride and chlorine.

Example 45 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 16.7 parts by weight of alpha-mercapto-acetanilide dissolved in approximately 200 parts by weight of methylene chloride. While agitating the so-charged mass at about 0 C. is slowly added approximately 45 parts by Weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. Upon completion of the sulfuryl chloride addition, the mass is agitated for about two hours at about room temperature. Thereafter, the mass is stripped of volatiles under vacuum to give a solid residue Which residue is dissolved in petroleum ether solvent, crystallized by cooling the solution to about 70 degrees centigrade, separated from the solvent by filtration and identified as alpha,alpha-dichloro-alpha-(chloromercapto)-acetanilide (melting point of 71 to 76 degrees Centigrade.)

Alpa,alpha dichloro alpha (chloromercapto)-acetanilide exhibits pre-emergent herbicidal activity against Canada thistle, lambsquarter and quackgrass.

Example 46 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 26.3 parts by weight of alpha-mercapto-4-chloroacetanilide dissolved in approximately 200 parts by Weight of methylene chloride. While agitating the so-charged mass at about 0 C. is slowly added approximately 35 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. Upon completion of the sulfuryl chloride addition, the mass is agitated for about two hours at about room temperature. Thereafter, the mass is stripped of volatiles under vacuum to give a liquid residue which residue is dissolved in petroleum ether solvent, crystallized by cooling the solution to about 70 degrees centigrade, separated from the solvent by filtration and identified as alpha,alpha,4' trichloro alpha-(chloromercapto)-acetaniliode (melting point of 71 to 73 degrees centigrade).

Alpha,alpha,4 trichloro alpha (chloromercapto)- acetanilide, exhibits pre-emergent herbicidal activity against Canada thistle and contact herbicidal activity against lambsquarter and barnyard grass.

Example 47 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 47 parts by weight of alpha-mercapto-meta-trifiuoromethylacetanilide dissolved in approximately 300 parts by weight of methylene chloride. While agitating the socharged mass at about 0 C. is slowly added approximately 81 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. Upon completion of the sulfuryl chloride addition, the mass is agitated for about two hours at room temperature. Thereafter, the mass is stripped of volatiles under vacuum to give a solid residue which residue is dissolved in petroleum ether solvent, crystallized by cooling the solution to about -70 degrees centigrade, separated from the solvent by filtration and identified as alpha,alpha-dichloro-alpha-(chloromercapto)-meta-trifluoromethylacetanilide (melting point of 60 to 62 degrees centigrade).

Alpha,alpha dichloro alpha-(chloromercapto)-metatrifluoromethylacetanilide exhibits pre-emergent herbi- 14 cidal activity against Canada thistle and Johnson grass and contact herbicidal activity against Canada thistle, cocklebur, morning glory, and lambsquarter.

Example 48 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 22 parts by weight of alpha-mercapto-Z',6 '-diethylacetanilide dissolved in approximately 300 parts by weight of 1,2-dichloroethane. While agitating the so-charged mass at about 0 C. is slowly added approximately 41 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. Upon completion of the sulfuryl chloride addition, the mass is agitated for about two hours at about room temperature. Thereafter, the mass is stripped of volatiles under vacuum to give a solid residue which residue is washed with pentane and identified as alpha,alpha dichloro alpha-(chloromercapto)-2,6-diethylacetanilide (melting point of 159 to 162 degrees centigrade).

Alpha,alpha dichloro alpha-(chloromercapto-2,6'- diethylacetanilide exhibits pre-emergent herbicidal activity against lambsquarter and downy brome.

Example 49 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 39 parts by weight of alpha-mercapto-Z',6'-dimethylacet anilide dissolved in approximately 300 parts by weight of chloroform. While agitating the so-charged mass at about 0 C. is slowly added approximately 81 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. Upon completion of the sulfuryl chloride addition, the mass is agitated for about two hours at room temperature. Thereafter, the mass is stripped of volatiles under vacuum to give a solid residue which residue is dissolved in carbon tetrachloride solvent, crystallized by cooling the solution to about 70 degrees centigrade, separated from the solvent by filtration and identified as alpha,alpha-dichloro-alpha-(chlorothio) 2,6 dimethylacetanilide (melting point of to 117 degrees centigrade).

Alpha,alpha-dichloro-alpha (chloromercapto) 2,6'- dimethylacetanilide exhibits pre-emergent herbicidal activity against Canada thistle and lambsquarter.

Example 50 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 39.4 parts by weight of alpha-mercapto-para-methoxyacetanilide dissolved in approximately 300 parts by weight of methylene chloride. While agitating the so-charged mass at about 0 C. is slowly added approximately 81 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. Upon completion of the sulfuryl chloride addition, the mass is agitated for about two hours at about room temperature. Thereafter, the mass is stripped of volatiles under vacuum to give a liquid residue which residue is dissolved in hot petroleum ether solvent, crystallized by cooling the solution to about 70 degrees centigrade, separated from the solvent by filtration and identified as alpha,alpha-dichloro-alpha-(chloromercapto)- para-methoxyacetanilide.

Alpha,alpha dichloro alpha (chloromercapto)-para methoxyacetanilide exhibits pre-emergent herbicidal activity against Canada thistle, lambsquarter and Johnson grass.

Example 51 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 76.4 parts by weight of alpha-mercapto-para-methylacetanilide. While agitating the so-charged mass at about C. is slowly added approximately 110 parts by weight of sulfuryl chloride. The reaction i exothermic and the temperature during the addition is permitted to rise to about C. Upon completion of the sulfuryl chloride addition, the mass is agitated for about two hours at about room temperature. Thereafter, the oily mass is extracted with petroleum ether solvent and a solid is crystallized by cooling the solution to about 70 degrees centigrade, separated from the solvent by filtration and identified as alpha,alpha dichloro alpha (chloromercapto)-paramethylacetanilide.

Alpha,alpha dichloro alpha (chloromercapto)-paramethylacetanilide exhibits pre-emergent herbicidal activity against Johnson grass.

Example 52 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 86 parts by weight of alpha-mercapto-para-bromoacetanilide dissolved in approximately 300 parts by weight of methylene chloride. While agitating the so-charged mass at about 0 C. is slowly added approximately 30 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. Upon completion of the sulfuryl chloride addition, the mass is agitated for about three hours at about room temperature. Thereafter, the mass is stripped of volatiles under vacuum to give a dark solid residue which residue is boiled with petroleum ether solvent for five minutes crystallized by cooling the solution to about 70 degrees Centigrade, separated from the solvent by filtration and after the fifth repetition of the extraction, identified as alpha,alpha-dichloro-alpha-(chloromercapto)-para-bromoacetanilide (melting point of 85 to 87 degrees centigrade) Example 53 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 16.3 parts by weight of alpha-(benzylmercapto)-2-tertbutyl-6'-methyl-acetanilide dissolved in approximately 200 parts by weight of methylene chloride. While agitating the so-charged mass at about 0 C. is slowly added approximately 20.1 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. Upon completion of the sulfuryl chloride addition, the mass is agitated for about two hours at about room temperature. Thereafter, the mass is stripped of volatiles under vacuum to give a solid residue which residue is Washed with petroleum ether and identified as alpha,alpha-dichloro-alpha- (2 tert butyl 6' methylbenzamido)methane sulfenyl chloride (melting point of 196 to 198 degrees centigrade).

Alpha,alpha-dichloro-alpha-(2'-tert-butyl 6' methylbenzamidohnethane sulfenyl chloride exhibits pre-emergent herbicidal activity against a wide range of species including Canada thistle, nutsedge, lambsquarter, smartweed, velvet leaf, bromegrass (cheat), and barnyard grass, as well as insecticidal activity against southern corn root worm.

Example 54 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 21.1 parts by weight of N,N-dimethyLalpha- (benzylmercapto)-acetamide dissolved in approximately 300 parts by weight of 1,2-dichloroethane. While agitating the so-charged mass at about 0 C. is slowly added approximately 40.2 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. Upon completion of the sulfuryl chloride addition, the mass is agitated for about one hour at above room temperature. Thereafter, the mass is stripped of volatiles under vacuum to give a liquid residue which residue is dissolved in petroleurn ether solvent, crystallized by cooling the solution to about 70 degrees centrigrade, separated from the solvent by filtration and identified as N,N-dimethyl-alpha, a]pha-dichloro-alpha-carbamoyl methane sulfenyl chloride (melting point of 47 to 48 degrees centrigrade).

N,N-dimethyl-alpha,alpha dichloro-alpha-carbamoyl methane sulfenyl chloride exhibits insecticidal activity against southern corn root worm.

Example 55 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 15.0 parts by weight of alpha-(benzylmercapto)- N-isopropylacetanilide dissolved in approximately 200 parts by weight of methylene chloride. While agitating the so-charged mass at about 0 C. is slowly added approximately 13.4 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. Upon completion of the sulfuryl chloride addition, the mass is agitated for about three hours at about room temperature. Thereafter, the mass is stripped of volatiles under vacuum to give a low melting solid residue. An additional 6 parts by weight of sulfuryl chloride and parts by weight methylene chloride is added and the mass is agitated overnight at room temperature. The mass is stripped of volatiles under vacuum to give a solid residue which residue is washed with petroleum ether solvent, and identified as alpha,alpha dichloro-alpha-(chloromercapto)-N-isopropylacetanilide (melting point of 121 to 122 degrees centigrade).

Alpha,alpha dichloro alpha (chlorothio) N isopropylacetanilide exhibits pre-emergent herbicidal activity against cocklebur, smartweed, nutsedge, quackgrass, downy brome, and barnyard grass as well as contact herbicidal activity against lambsquarter and Johnson grass.

Example 5 6 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 26.5 parts by weight of N,N-diisopropyl-alpha-(benzylmercapto)-actamide dissolved in approximately 200 parts by weight of methylene chloride. While agitating the socharged mass at about 0 C. is slowly added 40.2 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. Upon completion of the sulfuryl chloride addition, the mass is agitated for about one hour at about room temperature. Thereafter, the mass is stripped of volatiles under vacuum leaving a slurry to which slurry is added about 100 parts by weight of pentane. A precipitate forms which precipitate is separated from the pentane by filtration and identified as N,N-diisopropyl-alpha,alpha-dichloro-alpha carbamoyl methane sulfenyl chloride (melting point of 131 to 134 degrees centigrade N,N diisopropyl alpha,alpha dichloro alpha carbamoyl methane sulfenyl chloride exhibits insecticidal activity against southern corn root worm.

Example 57 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 18.1 parts by Weight of alpha-(benzylmercapto)-acetamide dissolved in approximately 200 parts by weight of methylene chloride. While agitating the so-charged mass at about 0 C. is slowly added approximately 40.2 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. 'Upon completion of the sulfuryl chloride addition, the mass is agitated for about one hour at about room temperature. Thereafter, the mass is stripped of volatiles under vacuum leaving a slurry which slurry is first washed with and then dissolved in petroleum ether solvent, crystallized by cooling the solution to about 70 17 degrees centigrade, separated from the solvent by filtration and identified as alpha,alpha-dichloro-alpha-carbamoyl methane sulfenyl chloride.

Example 5 8 To a suitable reaction vessel equipped with a thermometer, agitator and venting means is charged approximately 35.7 parts by weight of alpha-(benzylmercapto)- N-(methoxymethyl)-2',6'-diethylacetanilide dissolved in approximately 200 parts by weight of methylene chloride. While agitating the so-charged mass at about C. is slowly added approximately 40.2 parts by weight of sulfuryl chloride. The reaction is exothermic and the temperature during the addition is permitted to rise to about 20 C. 'Upon completion of the sulfuryl chloride addition, the mass is agitated overnight at about room temperature. Thereafter, the mass is stripped of volatiles under vacuum to give a liquid residue which residue is dissolved in petroleum ether solvent, crystallized by cooling the solution to about 70 degrees centigrade, separated from the solvent by filtration and identified as alpha, alpha dichloro alpha (chloromercapto) N (methoxymethyl)-2',6'-diethylacetanilide (melting point of 63 to 65 degrees centigrade).

Alpha,alpha-dichloro-alpha (chloromercapto)-N-(methoxymethyl)-2,6'diethylacetanilide exhibits pre-emergent herbicidal activity against Canada thistle, velvet leaf, morning glory, lambsquarter, smartsweed, nutsedge, quackgrass, bromegrass (cheat) and barnyard grass as well as insecticidal activity against southern corn root worm.

In similar fashion the alpha-(substituted carbamoyl)- alpha,alpha-dichloromethane sulfenyl chlorides of column B may be prepared from the substituted sulfides of column A and sulfuryl chloride in molecular proportion of at least 3 to 1 of sulfuryl chloride to substituted sulfide.

Alpha-(methyhnercapto)-N (methoxymethyl) -2,6-diethyl- Alpha,alpha-diehloro-alpha- (chloromercapto)-N-(methoxyacetamlide. methyl)-2,6-diethylacetani1ide. Alpha-(methylmercapto) Alpha,alpha-dichloro-alphaacetamide (chloromercapto)-aeetamide. Alpha-(methylmereapto) -N- Alpha,alpha-dichloro-alphaisopropylacetanilide. (chloromercapto)-N-isopropylaeetanilide. N,Ndimethyl-alpha,alpha-dichloro-alpha-carbamoyl methane suli'enyl chloride. Alpha,alpha-dichloro-alpha- (2-tert-butyl-6-methylbenzamido) -methane sulfenyl chloride. Alpha,alpha-dichloro-alpha- (chloromercapto) -4 -bron1oacetanillde. Alpha,alpha-diehloro-alpha- N,N-diemthyl-alpha-(methylmercapto)-acetamide.

Alpha- (methylrnercapto) -2-tertbutylfi-methyl acetanilide.

Alpha-(benzyhnercapto)4-bromoaeetanilide.

Al pha- (methylrnercapto) -2 ,6 -diacetannde. Alpha,alpha-dichl0ro-alpha- (chloromercapto)-N-cyclohexylacetanilide. Alpha,alpha-dichloro-alpha- (chloromercapto)-N-naphthylacetamide. Alpha,alpha-dichloro-alpha- (chloromercapto)-N,N-d1cy0lohexylacetamide.

Alpha,alphad.ichloro-alpha- Alpha-moronpto-N-eyclohexylacetam'lide.

Alpha-(methylmercapto) N- naphthyl-acetamide.

Alpha-(methylmercapto)-N,N-dieyclohexyl-acetamide.

Alpha-(methylmercapto)-N-2,6-

dinitrophenylacetamide. (chloromercapto)-N2,6dinitrophenyl-acetamide. Alpha-(m thylmercapto)- Alpha,alpha-diehloro-alphaacetanilide. (chloromercapto)-acetanilide. Alpha- (benzylrnercapto) -2 ,4 ,5 Alpha, alpha-dichloro-alphm chloroacetanilide. (chloromercapto) -2,4,5-tri- I ehloroacetanilide. Alpha (methylmercapto)-2',6-di- Alpha,alpha,dichloro-alpha- (trifluoromethyl)-acetanilide.

Alpha-(methylmercapto)-N,N-di- (methoxymethybacetamide.

Alpha-(methyhnercapto)-N,N-di- (tert-butyDacetamide.

(chloromercapto)-2,6-di- (trifluoromethyl)-aeetanilide. Alpha,alpha-dichloro-alpha- (chloromereapto)-N,N-d1- (methoxymethyl)-acetamide. Alpha,alpha-dichloro-alpha- (chloromercapto)-N,N-dl- (tert-butyDacetamide.

1 8 Example 59 The procedure of Example 45 is followed except that the reaction is carried out under reflux and instead of charging to the system 45 parts by weight of sulfuryl chloride, chlorine gas is bubbled through the refluxing mass until approximately 24 parts by weight thereof is absorbed. Alpha,alpha-dichlo'ro-alpha (chloromercapto)- acetanilide is obtained.

Example 60 The procedure of Example 46 is followed except that the reactionis carried out under reflux and instead of charging to the system 35 parts by Weight of sulfuryl chloride, chlorine gas is bubbled through the refluxing mass until approximately 18 parts by weight thereofis absorbed. Alpha,alpha,4'-trichloro-alpha-(chloromercapto)- acetanilide is obtained.

Example 61 The procedure of Example 47 is followed except that the reaction is carried out under reflux and instead of charging to the system 81 parts by weight of sulfuryl chloride, chlorine gas is bubbled through the refluxing mass until approximately 42 parts by weight thereof is absorbed. Alpha,alpha dichloro-alpha (chloromercapto)- meta-trifluoromethylacetanilide is obtained.

Example 62 The procedure of Example 48 is followed except that the reaction is carried out under reflux and instead of charging to the system 41 parts by weight of sulfuryl chloride, chlorine gas is bubbled through the refluxing mass until approximately 21 parts by weight thereof is absorbed. Alpha,alpha-dichloro-alpha-(chloromercapto)-2,6'- diethylacetanilide is obtained.

Example 63 The procedure of Example 49 is followed except that the reaction is carried out under reflux and instead of charging to the system 81 parts by weight of sulfuryl chloride, chlorine gas is bubbled through the refluxing mass until approximately 42 parts by weight thereof is absorbed. Alpha,alpha-dichloro-alpha-(chloromercapto)- 2,6'-dimethylacetanilide is obtained.

Example 64 The procedure of Example 50 is followed except that the reaction is carried out under reflux and instead of charging to the system 81 parts by weight of sulfuryl chloride, chlorine gas is bubbled through the refluxing mass until approximately 42 parts by weight thereof is sorbed. Alpha,alpha dichloro-alpha-(chloromercapto)- para-methoxyacetanilide is obtained.

Example 65 Example The procedure of- Example 52 isfollowed except that the =reactionis carried out under reflux and' instead of charging to the system 30 parts by weight of sulfuryl chloride, chlorine gas isbubbIed through the refluxing mass until approximately 16 parts by weight thereof is absorbed; 'Alpha;alpha{dic-hloro alph para bromoace'tanilide -*'is "obtained.

The procedurerof. Example 53' 15 followed except that the reaction is carr'iedout ui'1der" r'eflux a-nd' instead b charging to the systeni zoz-i parrs 'by'weight'of sulfury 19 chloride, chlorine gas is bubbled through the refluxing mass until approximately 11 parts by weight thereof is absorbed. Alpha,alpha-dichloro-alpha-(2' tert-butyl-6'- methylbenzamido)methane sulfenyl chloride is obtained.

Example 68 The procedure of Example 58 is followed except that the reaction is carried out under reflux and instead of charging to the system 40.2 parts by weight of sulfuryl chloride, chlorine gas is bubbled through the refluxing mass until approximately 21 parts by weight thereof is absorbed. Alpha,alpha-dichloroalphachloromercapto N-(methoxymethyl)-2',6'-diethy1acetanilide is obtained.

Example 69 To a suitable reaction vessel equipped with a thermo'meter, agitator and reflux condenser is charged approximately 5 parts by weight of alpha-(benzylthio)-N- isopropylacetanilide dissolved in approximately 100 parts by weight of methylene chloride. The so-charged mass is heated to reflux and While refluxing gaseous chlorine is sparged into the refluxing mass for about one hour. The mass is then stripped of volatiles to give a solid residue. The residue is washed with petroleum ether and identified as alpha,alpha dichloro-alpha-(chloromercapto)-N-isopropylacetanilide (melting point of 121-123 C.).

In similar fashion the alpha-(substituted carbamoyl) alpha,alpha-dichloro-methane sulfenyl chlorides of column B may be prepared from the substituted sulfides of column A and chlorine.

Alpha-(methylmercaptw-N- Al ha,alpha-dichloro-alpha methoxymethyD-2',6'-diethylchloromercapto)-N-(methoxyacetanillde. methyl)-2',6-diethylacetanilide. Alpha-(methylmereapto)- Alphmalphardichloro-alphaacetamide. (chloromercapto)-acetamide. Alpha-(methylmercapto)-N-1so- Alphanlphardichloro-alphar propylacetamlide. (chloromercapto)-Nisopropylacetanilide.

N ,N-dimethyl-alph a-(methylmercapto)-acetamide.

Alpha-(methylmercapto)-2'-tertbutyl-S-methylacetanilide.

N,N-dimethyl-alpha,alphadichloro-alpha-carbarnoyl methane sulfenyl chloride.

Alpha,alpha-diehloro-alpha-(2'- tert-butyl-fi'-methylbenzamido)- methane sulfenyl chloride.

Alphartbenzyhnercaptoy i" alphaalpha-dichloro-alphalbromoacetanilide. (chloromercapto)-4'-bromoacetanilide. Alpha-(methylmercapto)-2,6- Alpha,alpha-dichloro-alphachloroacetamlide. (chloromercapto)-2,6'-

dichloroacetanilide.

Alpha-(methylmereapto)-4- Al ha,alphn-diehlor0-alphamethylacetamlide. chloromercapto)-4-methylaceta-nilide. Alpha-(benzylmercapto)-3'- Al ha,a1pha-d.ichloro-alphaethylacetanilide. chloromereapto)-3et-hylacetanilide. Alpha-(benzylmercapto)-N- Al ha,alpha diohloro-alphacyclopentylacetamide. hloromeroaptm-N-cyclopentylacetami de. Alpha,alpha-dichloro-alpha- (chloromercapto)-N-cyclohexylacetanilide. Alphaalpha-dichloro-alpha- Alpharmercapto-N-cyclohexylacetanilide.

Alpha-(methylmereapto)-N- trichloroacetanilide. Al ha,alpha-chloro-alphachloromerca to)-3,5-di(trlfluoromethyl -acetanilide. Alpha,alpha-dichloro-alpha- (chloromereapto)-N,N- di(methcxymethyD-acetamde.

Alpha(methylmercapto)-3',5-

di(trifluoromethyl) acetanllide.

Alpha-(methylmereapto)-N,N-

di(methoxymethyl)-acetamide.

Alpha-(methylmercapto)N,N- Alpha,alpha-dichloro-alphadi(tert-butyl)-acetamide. (ebiorornercapto)-N,N- B di(tert-butyl)-acetamide.

Example The procedure for testing post-emergence herbicidal 70 activity of various compounds of this invention is as follows. The active ingredients are applied in spray form to 28 day old specimens of various plant species. The spray, an acetone-water solution containing active ingredient and a surfactant (65 parts tall oil condensed with ethylene oxide in the ratio of 11 moles ethylene oxide to 1 mole tall oil) is applied to the plants in different sets of pans at a rate of 3.6 pounds per acre of active ingredient. The treated plants are placed in a greenhouse and the effects are observed and recorded after approximately 14 days or approximately 28 days.

Example 71 The procedure for testing pre-emergent herbicidal activity of representative alpha-carbamoyl-alpha,alpha-dichloro-methanesulfenyl chlorides of this invention and their intermediaries is as follows:

A good grade of top soil is placed in aluminum pans and compacted to a depth of to [2 inch from the top of the pan. A predetermined number of seeds of each of several plant species are placed on top of the soil in the pans. The seeds are covered with soil and the pans leveled. The herbicidal composition is applied by spraying the surface of the top layer of soil with a solution containing a sufficient amount of active ingredient to obtain a rate of application of 5 lbs. per acre. The pans are then placed on a sand bench in the greenhouse and watered from below as needed. The plants are observed at the end of approximately 14 days and the results recorded.

Example 72 The procedure for testing insecticidal activity of representative alpha carbamoyl alpha,alpha-dichloromethane sulfenyl chlorides and intermediate products of this invention against the southern corn root worm is as follows:

To a growth pouch (diSPo Seed-Pal: growth pouch, catalog No. B1220, of Scientific Products Division of American Hospital Supply Corporation, Evanston, Ill.) in an upright position is added 20 ml. of distilled water. Thereafter is added 0.1 ml. of an acetone solution of known concentration in percent by weight of a compound of this invention (for example a 0.1 ml. of a 0.1% by weight acetone solution of the compound provides a concentration of 5.0 ppm. thereof). In the trough of the pouch formed by the paper wick thereof are placed two corn seeds (Zea mays, Hybrid US. 13) about one inch apart. Thereupon to the trough and between the seeds is added 8 to 12 ready-to-hatch eggs of the southern corn root worm (Diabrotica undecimpunctata howardi) which eggs are washed (with distilled water) free of the soil in which they are incubated at room temperature for 21 days immediately prior to their placement in the trough. The so-charged growth pouch is then placed in an upright position in an incubator maintained at F. and 70% relative humidity for 14 days. Immediately thereafter growth pouches are removed and the extent of kill of the corn rootworm larvae is observed.

While this invention has been described with respect to certain embodiments it is to be understood that it is not so limited and that variations and modifications thereof obvious to those skilled in the art to which this invention appertains can be made without departing from the spirit or scope thereof.

What is claimed is:

1. An alpha,alpha-dichloro-methane sulfenyl chloride of the formula and A is alkylene of the empirical formula C H wherein n is a whole number from 4 to 8, inclusive, and having 21 from 4 to 8 carbon atoms in a continuous chain between the terminal valence bonds, B is hydrogen, alkyl of from 1 to 5 carbon atoms, alkoxyalkyl of from 2 to 6 carbon atoms, cyclopentyl, cyclohexyl, naphthyl, phenyl or substituted phenyl wherein the ring substituents thereof total from 1 to 3 which substituents are from to 3 alkyl of from 1 to 6 carbon atoms, from 0 to 2 alkoxy of from 1 to 6 carbon atoms, from 0 to 3 halogen of atomic weight in the range of 18 to 80, from 0 to 2 nitro, from O to 1 cyano, or from 0 to 2 trifluoromethyl and D is hydrogen, alkyl of from 1 to 5 carbon atoms, alkoxyalkyl of from 2 to 6 carbon atoms, cyclopentyl, cyclohexyl, naphthyl, phenyl and substituted phenyl wherein the ring substituents thereof total from 1 to 3, which substituents are from 0 to 3 alkyl of from 1 to 6 carbon atoms, from 0 to 2 alkoxy of from 1 to 6 carbon atoms, from 0 to 3 halogen of atomic weight in the range of 18 to 80, from 0 to 2 nitro, from 0 to 1 cyano, or from 0 to 2 trifiuoromethyl.

2. A compound of claim 1. wherein B and D are like alkyl of from 1 to 5 carbon atoms.

3. The compound of claim 2 wherein B and D are methyl.

4. The compound of claim 2 wherein B and D are isopropyl.

5. A compound of claim 1 wherein B is primary alkyl of from 1 to 5 carbon atoms and wherein D is alkoxyalkyl of 3 carbon atoms.

6. The compound of claim 1 wherein B is ethyl and wherein D is 3-isopropoxypropyl.

7. A compound of claim 1 wherein B and D are like alkoxyalkyl of from 2 to 6 carbon atoms.

8. The compound of claim 7 wherein B and D are 3- isopropoxypropyl.

9. The compound of claim 1 wherein B and D are hydrogen.

10. A compound of claim 1 wherein B is alkyl of from 1 to 5 carbon atoms and wherein D is phenyl.

11. The compound of claim 10 wherein B is isopropyl.

12. A compound of claim 1 wherein B is alkoxyalkyl of from 2 to 6 carbon atoms and wherein D is di-substituted phenyl, the two ring substituents thereof being alkyl of from 1 to 6 carbon atoms.

13.. A compound of claim 12 wherein D is 2,6-di-substituted phenyl.

14. A compound of claim 12 wherein D is 2,6-diethylphenyl.

15. The compound of claim 14 wherein B is methoxymethyl.

16. A compound of claim 1 wherein B is hydrogen and D is a substituted phenyl of the formula wherein X is selected from the group consisting of halo and tert.a1kyl of from 4 to 6 carbon atoms, wherein Y is selected from the group consisting of halo and primary and secondary alkyl respectively having not more than 4 carbon atoms and wherein Z is selected from the group consisting of halo, hydrogen and primary and secondary alkyl having not more than 4 carbon atoms.

17. A compound of claim 16 wherein X is tert-butyl, wherein Y is primary alkyl and wherein Z is hydrogen.

18. The compound of claim 17 wherein Y is methyl.

19. The compound of claim 1.7 wherein Y is ethyl.

20. A compound of claim 1 wherein B is hydrogen and D- is (ii-substituted phenyl, the two ring substituents thereof being alkyl of from 1 to 6 carbon atoms.

21. A compound of claim 20 wherein D is 2,6-di-substituted phenyl.

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Phillips et al.: J. Org. Chem. (1971), vol. 36, No. 21, pp. 31459.

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LORRAINE A. WEINBERGER, Primary Examiner R. D. KELLY, Assistant Examiner US. Cl. X.R.

260239 BF, 293.85, 326.5, 465 D, 558 S, 561 S, 562 S; 424244, 267, 274, 315 

